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The prevention of ferrocene leakage from an electrode by physical retention of mediator in a cellulose acetate membrane matrix is reported here for the first time. Five types of cellulose acetate membranes were prepared, containing 1.8, 5.3, 8.5, and 20.0% of ferrocene and a membrane containing 1.8% of ferrocene and 0.05% of Nafion in the matrix. All the membranes tested, including a cellulose acetate membrane without ferrocene, were much more resistant to ascorbate interference (12-69 nA mM-1) in comparison to an uncovered glassy carbon electrode (1152 nA mM-1). With increasing amount of ferrocene in the membrane, a decreasing ability of the membrane to retain mediator was observed. Ferrocene-embedded membranes were successfully applied in the construction of a fructose biosensor by immobilisation of PQQ-dependent fructose dehydrogenase. A biosensor with a membrane containing 20.0% of ferrocene in the matrix exhibited the lowest detection limit (3 muM), the shortest response time (45 s) and the highest sensitivity (232 nA mM-1). However, this biosensor was unstable because of ferrocene leaching and after 9 h of continuous use only 15% of the initial activity was observed. The biosensor with a cellulose acetate membrane containing 1.8% of ferrocene and 0.05% of Nafion had better stability characteristics, and retained almost 40% of the initial response after 8 h of continuous use, with similar sensitivity (226 nA mM-1) and response time (75 s).

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The attempted coupling of (ferrocenylmethyl)trimethylammonium iodide (1) with 1,4,7-(triformyl)-1,4,7,10-tetraazacyclododecane (2) in water led to the formation of the expected compound 1-(ferrocenemethyl)-4,7,10-(triformyl)-1,4,7,10-tetraazacyclododecane (3). In addition, hydrolysis of the ferrocenyl precursor 1 led to the formation of two other known compounds, hydroxymethylferrocene (4) and bis(ferrocenylmethyl) ether (5). An X-ray crystal structure determination of 4 revealed the presence of H-bonding between the hydroxyl groups of one molecule of 4 and the oxygen atom of an adjacent molecule resulting in a left-handed helical chain of molecules lying along the b-axis direction. The O?O distances are significantly shorter than those found in previously reported structures of hydroxymethylferrocene derivatives indicative of moderate strength H-bonding interactions. In the structure of 5, the orientation of the ferrocenyl groups are staggered relative to a vector comprising the two carbons of the C-O-C linker. Crown Copyright

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Reference:
Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Hydrosilylation of aldehydes and ketones catalysed by nickel acetate and tricyclohexylphosphine as the catalytic system was demonstrated using polymethylhydrosiloxane as a cheap reducing reagent. The Royal Society of Chemistry 2013.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Presented herein is a simple, robust, and label-free homogeneous electrochemical sensing platform constructed for the detection of protein kinase activity and inhibition by integration of carboxypeptidase Y (CPY)-assisted peptide cleavage reaction and vertically ordered mesoporous silica films (MSFs). In this sensing platform, the substrate peptide composed of kinase-specific recognized sequence and multiple positively charged arginine (R) residues was ingeniously designed. In the presence of protein kinase, the substrate peptide was phosphorylated and then immediately resisted CPY cleavage. The phosphorylated peptide could be effectively adsorbed on the negatively charged surface of MSFs modified indium-tin oxide (ITO) electrode (MSFs/ITO) by noncovalent electrostatic attraction. The adsorbed peptide was subsequently used as a hamper to prevent the diffusion of electroactive probe (FcMeOH) to the electrode surface through the vertically aligned nanopores, resulting in a detectable reduction of electrochemical signal. As demonstrated for the feasibility and universality of the sensing platform, both protein kinase A (PKA) and casein kinase II (CK2) were selected as the models, and the detection limits were determined to be 0.083 and 0.095 UmL-1, respectively. This sensing platform had the merits of simplicity, easy manipulation, and improved phosphorylation and cleavage efficiency, which benefited from homogeneous solution reactions without sophisticated modification or immobilization procedures. In addition, given the key role of inhibition and protein kinase activity detection in cell lysates, this proposed sensing platform showed great potential in kinase-related bioanalysis and clinical biomedicine.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Fc (ferrocene)-functionalized citric acid dendrimers were successfully synthesized via the reaction of citric acid dendrimers with ferrocene methanol using dicyclohexylcarbodiimide. ClOC?PEG?COCl was used as the core, and the related dendrimers were synthesized divergently. Subsequently, each generation was functionalized with ferrocene methanol. The obtained Fc-dendrimers were characterized by 1H NMR and FTIR spectroscopy. We have studied the relocation of electrons around the peripheries of dendrimers and between their redox terminals and electrodes by studies of the electrochemistry of dendrimers awarding metallocenes as functional?s groups, because these compounds can be stabilized together their oxidized and their reduced states. In addition, the voltammograms of each Fc-functionalized generation were studied and the influence of scan rate, solvent, and [Fe] unit and the concentration of the Fc-dendrimers were investigated.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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A description of the preparation and characterization of 25 mum diameter modified carbon paste-based Cu2+ ion-selective electrodes are reported. The electrodes have a linear potential response within the 10-3 to 10-6 M range and a 16 s response time. A substantial benefit of this new type of ion-selective microelectrode (ISME) is the capability to use them as a dual function tip, in either the amperometric or the potentiometric mode of scanning electrochemical microscopy (SECM). The applications reported also support the usefulness of copper ion-selective carbon paste microelectrodes in SECM potentiometric imaging.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The technology provided herein relates to novel variants of microbial glucose oxidase with improved properties, more specifically to polypeptides having glucose oxidase activity as their major enzymatic activity; to nucleic acid molecules encoding said glucose oxidases; vectors and host cells containing the nucleic acids and methods for producing the glucose oxidase; compositions comprising said glucose oxidase; methods for the preparation and production of such enzymes; and to methods for using such enzymes for food and feed processing, for the measurement of free glucose in clinical samples and bioreactors, and the development of miniature biofuel cells.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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Allylic and benzylic alcohols can be selectively oxidized to their corresponding aldehydes or ketones in water containing nanoreactors composed of the designer surfactant TPGS-750-M. The oxidation relies on catalytic amounts of CuBr, bpy, and TEMPO, with N-methyl-imidazole; air is the stoichiometric oxidant. the Partner Organisations 2014.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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The aim of this work is to explore the applicability of the scanning electrochemical microscope (SECM) to characterize the inhibiting effect of 2-mercaptobenzimidazole against the corrosion of copper. SECM was operated in the feedback mode by using ferrocene-methanol as redox mediator, and the sample was left unbiased at all times. The kinetic changes in the corrosion processes were monitored over time from the Z-approach curves. Furthermore, inhibitor-modified copper samples presenting various surface finishes were imaged by SECM and the scanning vibrating electrode technique (SVET), allowing changes both in the surface activity of metal-inhibitor films and in the extent of corrosion attack to be spatially resolved. Differences in the local electrochemical activity between inhibitor-free and inhibitor-covered areas of the sample were successfully monitored.

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion

 

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This review (with 210 references) summarizes recent developments in the design of voltammetric chemical sensors and biosensors based on the use of carbon nanomaterials (CNMs). It is divided into subsections starting with an introduction into the field and a description of its current state. This is followed by a large section on various types of voltammetric sensors and biosensors using CNMs with subsections on sensors based on the use of carbon nanotubes, graphene, graphene oxides, graphene nanoribbons, fullerenes, ionic liquid composites with CNMs, carbon nanohorns, diamond nanoparticles, carbon dots, carbon nanofibers and mesoporous carbon. The third section gives conclusion and an outlook. Tables are presented on the application of such sensors to voltammetric detection of neurotransmitters, metabolites, dietary minerals, proteins, heavy metals, gaseous molecules, pharmaceuticals, environmental pollutants, food, beverages, cosmetics, commercial goods and drugs of abuse. The authors also describe advanced approaches for the fabrication of robust functional carbon nano(bio)sensors for voltammetric quantification of multiple targets. [Figure not available: see fulltext.].

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Iron Catalysis in Organic Synthesis | Chemical Reviews,
Iron Catalysis in Organic Synthesis: A Critical Assessment of What It Takes To Make This Base Metal a Multitasking Champion